Quaternary ammonium halides



Unitid matent 2,775,604 QUATERNARY AMMONIUM HALIDES John David Zech,Wilmington, DeL, assignor to Atlas Powder Company, Wilmington, DeL, acorporation of Delaware No Drawing. Application February 9, 1953,

Serial No. 336,005 1 14 Claims. (Cl. 2 60-4045) -.'lhe present inventionrelatesjto newprganic ammonium compounds and relates more particularlyto quaternary ammonium halides which are suitable for various uses asWetting agents, detergents, emulsifying agents,

germicides, fungicides, anti-static agents, teirtile assistants,

textile lubricants, corrosion inhibitors','-'lnbricant additives, moldrelease agents, chemical intermediates, and the like.

his an object of -the present invention to prepare-surfacewactivequaternary ammonium halides havingwthree t or more free hydroxyl groups.It is a further object to prepare cationic surface active agents, 1 :byth quat erniza tionof tertiary amin'es, havingiat least one long; chainalkyl group with the condensates of epihalohydrins with polyhydricalcohols having at least three hydr'oXyl groups l or polyoxyalkyleneethers of said polyhydric alcohols.

Further objects and advantages will become obviousto R=hydroxyl freeresidue of apolyol having 3 to 6, OH groups om 3 to 1,0 c r onptbms '0 I=1 to.6 but'not greater than theQnumbLer j'of groups in the polyol lz=number of original OH groups in p o'lyol less w l vw+yz=not greaterthan R1=a lipophilic radical with 6 to' carbon atoms R2 and Rsareselected from. thegroup consistingo f lower .alkyl radicals and loweraliphatic radicals whichio- 'gether withN form a heterocyclic; ring YX=.:h 0g v i t Atypical compoundof this elassinaybe represented by theformula" (spatial configuration being ignored) This t compound 'niayicpnsideredas lauryl dimethyl amine quaternized with the eornpoun lCHzQCHzOHtOEDCHiCl ono'nni which is the addition product ofahexitol and'epichloro hydrin. With reference to the generic formula above 2,775,604Patented Dec. 25, 1956 -2 R is the residue of ahexahydric alcohol v is 0t y isO z is S 0 w is 1 vw-l-yz is 0 R1 is C12H25 R2 and Rs are CH3 XisCl Thc definition of R1 as a ilipophilic radical with 6 to 25 carbonatoms is meantto incl ude a hydrocarbon radical or an alkylsubstitutedaralkyl radicalwhere thealkyl substituent is a hydrocarbongroup containing from 6'I'to RQOH 18 carbon atoms such'as 0 RQ-CHzor 18carbon wherein R is'a hydrocarbon group of ,6 ,to atoms.

Within the s n ti n 9 B are @1 9 t b .includs [wherein-R is ahydrocarbonradical of 6 or more carbon atoms. :Iertiary aminescontaining such a group, for the purposes of this invention, would becarboXylic acid esters of dialkyl amino-alkanols.

In the preferred method for making the compounds of the invention anepihalohydrin such as epichlorohydrin is first condensed with apolyhydric alcohol having at least three hydroxyl groups. Among thepolyhydric alcohols; that are. suitable-for this purpose. are, suchalcohols as sorbitol, mannitol, erythritol, glycerol, diglycerol,triglycerol, pentaerythritol, dipentaerythritol, etc. Not only may thepolyhydric alcohols themselves be condensed with the epihalohydring bptthe polyoxyalkylene ethers of said polyhydric "alcohols may also becondensed with. the epihalohydrins, such as hydroxy, polyoxyethylenesorbitol, hydroxy polyoxyethylene' glycerol, hydroxy polyoXypropyleneglycerol, hydroxy polyoxyethylene pentaerythritolphydroxypolyokyethylene, diglycerol, etc. The number 'of,oxyalkylene groups permoleof polyol may vary widely, but those compounds are preferred whereinthe number of polyoxyalkylene groups ranges from T1 to lOQmQlesper moIeat polyol. The condensation of the epihalohydrin and the polyhydricalcohol or a polyoxyalkylene ether of saidalc ohol, takes place in thepresence of an acidic type of catalyst, such as AlCl3, BFs, SnClr, etc.,yielding the corresponding glyceryl monochlorohydrin etherofsaid-polyhydric alcohol'or of a polyoxyalkylene ether offsaidpolyhydricalcohol. Either a glyceryl monochlo rohydrin".monoether may beformed or a gly ceryl mon'ochlorohydr'inpolyether may be formeddepending primarily on the molanproportions of the starting "materials.The m brtmwor the above reactants may vary widely but the preferredrangeis from about 1 to 2 moles of 'epi halohydrin per mole ofpolyhydric alcohol or polyoxyalkylene ether of said polyhydric alcohol.The above" c'ondensation reaction is exothermic'and is controlledby thegradual addition of the epihalohydrin to the'polyol which also containsthe selected acidic type catalyst. These condensates thus formed arethen reacted with a suitable tertiary amine having at least onelong-chain alkyl group or anlalkyl aryl' group wherein s aid alkylradical is along chain aliphatic radical at a temperature of about CI to.1350. C I q t, m

The preferred tertiary amines are those having a mini- 7 mum sterichinderance at the tertiary N atom. Suitable benzoic, capryllicpelargonic capric, lauric,.. palmitic,

stearic, oleic, behenic, erucic, lin'oleic, tall oil, rosin, etc.

Alkyl morpholines such as cetyl morpholine, 2-rnorpholinoethyl stearate,etc., maybe used, but are somewhat less'reactive due to sterichindrance. I

Tertiary amines of the general'formula' of anhydrous sorbitol in thepresence of 1.4 cc. of BF: etherate in the same manner as outlined inpart A of this example. The product was similar in its characteristicsto that obtained in part A. It was a mixture of chlorohydrin ethers ofsorbitol containing an average of 1.5 chlorohydrin groups per mole.

Quaternary ammonium compounds prepared from the above condensates wereprepared in the below examples in the following manner.

The reactants were charged into a suitable flask fitted with a stirrerand a thermometer, and the reactants were then heated with vigorousagitation at the specified temperatures for the indicated periods oftime. Initially the reactants were immiscible. and as the reactionproceeded the mixture gradually became homogeneous except in thereaction with cetyl morpholine which reaction was only partiallycomplete, even after a fairly long reaction period at temperatures above130 C. As the reaction progressed the viscosity of the reaction mixturesincreased markedly.

Gms. of l Epi- Eplchlorohydrin Gms. of Reaction Reaction Example chloro-Condensate Tertiary Tertiary Amine Time snap Nature of Product hydrinine I in hours v v Condensate 185 Example I, Part A 213Laury1DimethylAmine---.-- 5% 109-121 Soft waxy solid water soluble. 206Example I, Part B 157 do 2V 112-130 o. 160 Example I, Part 0.. 157 do 3%2 30. t 1

p se sys em, W6! VXSCOUS 172 cetyl Morphonne 8 131-164 layer amounted to235 gms. 227 octadecyl Dimethyl Amine 2 102-133 Waxy solid watersoluble. 350 Dimethyl Aminoethyl Stearate.. 4V 107-126 Do. 319 2 hydroxy5 dodecyl Benzyl 24 114-130 Resinous solid.

Dlmethyl Amine. v

35 The foregoing examples exemplify the quatemization of 0( N a tertiaryamine with a condensate of an epihalohydrin and a polyol having at leastthree hydroxyl groups.

wherein R=a higher alkyl radical containing from to carbon atoms R1 andR2 are lower alkyl groups to hard waxy substances which are watersoluble,forming A viscous foaming solutions. The multiplicity of freehydroxyl groups is believed to favor their strong adsorption onsurfaces.

The following examples are given as best illustrating the invention andare notto be taken as limiting the i invention in any way.

Example I The following epichlorohydrin-sorbital condensate wereprepared in the manner depicted.-

A. 530 g. of epichlorohydrin was added dropwise with stirring to 522 g.molten anhydrous sorbitol containing 1 cc. of BF3 etherate (48% BF3)during 1 hourat 105l18 C. The reaction was exothermic. Stirring wascontinued 20 minutes during which time the temperature dropped to 85 C.The product was a very viscous, nearly colorless syrup at roomtemperature. It was a chlorohydrin ether of sorbitol containing anaverage of two chlorohydrin groups per mole.

B. 370 g. of epichlorohydrin was reacted with 733 g.

etherate in the same manner as outlined in part A of this example. Theproduct .was similar in its physical characteristics to that obtained inpart A. It was a chlorohydrin ether of sorbitol containingonechlorohydrin'group m methylamine with vigorous agitation and heatingfrom per mole.

C. 555 g. of epichlorohyd rin was reacted The following examplesexemplify the quaternization of a tertiary amine with the condensate ofan epihalohydrin and a polyoxyalkylene ether of an aliphatic polyolhaving at least three hydroxyl groups.

Example 9 270 parts of 2 polyoxyethylene sorbitol and 1 part of BFaetherate were heated to 100 C. and 135 parts of epichlorohydrin wereadded with stirring during 30 minutes keeping the temperature at 100 to110 C. The mixture was stirred for another hour at 100 to 110 C. toinsure complete reaction. The product was a viscous syrup, which wasreacted with 269 parts of cetyl dimethylamine with vigorous agitationand heating for 4% hours at 90 to 135 C. to yield the correspondingquaternary ammonium compound.

Example 10 304 parts of 2 polyoxypropylene sorbitol and 1 part ofBFs'etlierate were heated to 100 C. and 135 parts of epichlorohydrinwere added with stirring during 30 z minutes keeping the temperature at100 to 110 C. to

insure complete reaction. The product, a viscous syrup, was then reactedwith 295 parts of octadecenyl dimethylamine for 3?: hours at atemperature ranging from 110 C. to 135 ;C. to yield the correspondingquaternary amr monium compound.

Example 11 446 parts of 6 polyoxyethylene sorbitol and 1 part of BF:etheratewere heated to C. and 135 parts of epichlorohydrin were addedwith stirring during 30 minof anhydrous sorbitol 1n the presence of 1.4cc. of BF3 utes keeping the temperature at 100 to C. The mixture wasstirred for another hour at 100 to 110 C. to insure complete reaction.The product, a viscous syrup, was then reacted with 297 parts ofoctadecyl di- 112. to C. toyield; the'corresponding quaternary ip fi .1:L..

'5 Example 12 =518pparts of 6 polyoxypropylenesorbitol and 1 part of BF3etherate were heated to 100 .C. and 185 parts of epichlorohydrin wereaddedwithstirring during 30 minutes, keeping the temperature at 100 to110 C. to insure complete reaction. Theproduct, a viscous syrup, wasthen reacted with 213 parts of lauryl dimethylamine with vigorousagitation and heatingfrom 95 to 135 C for 3 /2 hours to yield thecorresponding quaternary amine. v o i It will be understood that theembodiments of the invention described in the specification andillustrated by the examples are only illustratiyeof the compounds andthe manner in whioh they agesproduced. Various modifications can ben adewithout departing from the principles of the invention.

.What is claimedis:

1. A chemical compound of the formula:

wherein:

R=the hydroxyl free residue of a hexitol w=1 to 6 z=6w R1=an alkylradical with 6 to 25 carbon atoms R2 and R3 are lower alkyl radicals X=ahalide 2. A chemical compound of the formula:

X\1lti R|:OCH2OH0HCHz1 T-R2]w Ra 11). wherein:

R=the hydroxyl free residue of a hexitol w=1 to 6 z=6-w R1=a lipophilicradical of from 6 to 25 carbon atoms containing an alkyl group of from 6to 18 carbon atoms R2 and R3 are lower alkyl radicals X=a halide 3. Acompound of the formula of claim 2 wherein the radical X B1 NR 1'1.

01 CQHtOOCCYJHSG NCH3 CH3 4. A chemical compound of the formula V X B1 RO(C,.H2n0)'OH2OH0HO1;2l IR2]w in [0 onmnonm.

R is the hydroxyl free residue of a hexitol n is 2 to 3 y is O to v is 0to 10 w is 1 to 6 z is 0 to 6 vw+yz=not greater than 10 R1 is alipophilic radical of from 6 to 25 carbon atoms containing an alkylgroup of from 16 to 18 carbon atoms R2 and R3 are lower alkyl radicals xis a halide 5. A compound as described in claim 4 wherein R1 is analiphatic radical with 6 to 25 carbon atoms. 6. The compounds of claim 4wherein is dimethyl lauryl amine.

7. The compounds of claim 4 wherein is dimethyl cetyl amine.

8. Thecompounds of claim 4 wherein $1 IIF-Rz R:

is dimethyl octadecyl amine.

9. The compounds of claim 4 wherein is dimethyl amino ethyl stearate.

10. The compounds of claim 4 wherein N-Rz It.

is dimethyl amino ethyl oleatel 11. The process of preparing quaternaryammonium halides which comprises reacting an epihalohydrin with apolyhydroxylic compound of the formula:

wherein:

R is the hydroxyl free residue of a hexitol n=2 to 3 v=0 to 10 in thepresence of an acidic type catalyst to produce a glycerol halohydrinether of said polyhydroxylic compound, and then reacting said ether witha tertiary amine of the formula:

'32 R1""'N" R3 wherein:

R1 is a lipophilic radical of from 6 to 25 carbon atoms containing analkyl group 'of from 6 to 18 carbon atoms R2 and R3 are alkyl radicalsto form a quaternary ammonium halide.

12. The process of preparing quaternary ammonium halides which comprisesreacting an epihalohydrin with polyhydroxylic compound of the formula:

R[O(O1|H2:1O)'H]6 wherein:

R is the hydroxyl free residue of a hexitol 11:2 to 3 v-=0 to 10 in thepresence of an acidic type catalyst, to yield 2. glycerol halohydrinether of said polyhdroxylic compound, and thereafter reacting said etherwith a tertiary amine of the formula:

Ilia R1NR3 wherein:

at a temperature of 90 to 135 C. to yield a quaternary ammonium halide.

13. The process of preparing quaternary ammonium halides which comprisesreacting an epihalohydrin with a hexitol in the presence of'BFs'as acatalyst, to produce 9. glycerol halohydriu ether of the hexitol andthen re- 2 molecular proportions of epichlorohydrin to produce aglycerol chlorohydrin ether of'sorbitol, and thereafter reacting saidether with a tertiary amine having one long chain aliphatic radical of 6to 25 carbon atoms and two short chain aliphatic radicals 'of 1 to 4carbon atoms to produce the quaternary ammonium chloride.

References Cited in the file of this patent UNITED STATES PATENTS 102,060,850 Calcott et al. Nov. 17, 1936 2,087,506 De Groote July 20, 19372,255,252 Harris Sept. 9, 1941 2,483,749 Wittcotf Oct. 4, 1949 2,547,965Olin Apr. 10, 1951 15 2,653,156 Deutsch et a1. -Sept. 22, 1953 FOREIGNPATENTS 538,718 Great Britain Aug. '14, 1941

1. A CHEMICAL COMPOUND OF THE FORMULA: